JP6562629B2 - パルスプラズマ暴露を伴うプラズマ原子層堆積 - Google Patents
パルスプラズマ暴露を伴うプラズマ原子層堆積 Download PDFInfo
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- JP6562629B2 JP6562629B2 JP2014262248A JP2014262248A JP6562629B2 JP 6562629 B2 JP6562629 B2 JP 6562629B2 JP 2014262248 A JP2014262248 A JP 2014262248A JP 2014262248 A JP2014262248 A JP 2014262248A JP 6562629 B2 JP6562629 B2 JP 6562629B2
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- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 1
- LFKDJXLFVYVEFG-UHFFFAOYSA-N tert-butyl carbamate Chemical compound CC(C)(C)OC(N)=O LFKDJXLFVYVEFG-UHFFFAOYSA-N 0.000 description 1
- UTYRQCFTOYUATF-UHFFFAOYSA-N tert-butyl(chloro)silane Chemical compound CC(C)(C)[SiH2]Cl UTYRQCFTOYUATF-UHFFFAOYSA-N 0.000 description 1
- IPGXXWZOPBFRIZ-UHFFFAOYSA-N tert-butyl(silyl)silane Chemical compound CC(C)(C)[SiH2][SiH3] IPGXXWZOPBFRIZ-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- KNSVRQSOPKYFJN-UHFFFAOYSA-N tert-butylsilicon Chemical compound CC(C)(C)[Si] KNSVRQSOPKYFJN-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- VOSJXMPCFODQAR-UHFFFAOYSA-N trisilylamine group Chemical group [SiH3]N([SiH3])[SiH3] VOSJXMPCFODQAR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02532—Silicon, silicon germanium, germanium
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
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Description
本出願は、2013年12月30日に出願された、発明の名称を「PLASMA ENHANCED ATOMIC LAYER DEPOSITION WITH PULSED PLASMA EXPOSURE(パルスプラズマ暴露を伴うプラズマ原子層堆積)」とする米国特許出願第14/144,107号に基づく優先権を主張する。
パルスプラズマ処理は、プラズマの高周波数RF電力及び/又は低周波数RF電力をパルス化することができる高周波数RF発生器を使用して、既存の半導体処理機器によって実施することができる。具体的には、カリフォルニア州のフリーモント市のLam Research Corporationから市販されているVector(商標)リアクタなどのリアクタが、パルスPEALDに使用されてよい。こうして、最小のハードウェア変更によって、膜の改善がなされる。
実験結果は、開示されるプロセスが、均一な高品質の膜を実現するために使用されえることを示している。図5Aと図5B、及び図6Aと図6Bは、半導体基板上の溝内に堆積されたシリコン炭窒化物膜の、堆積されたままの状態の、及び100:1の水:HFの中で90秒間にわたってエッチングした後における断面図を示している。図5C及び図6Cは、図5Aと図5B、及び図6Aと図6Bに示された膜のエッチング特性に関する表をそれぞれ示している。
適用例1:半導体基板表面上のギャップを満たす方法であって、
(a)その中に前記基板を有する反応チャンバに気相の第1の反応物を導入し、前記第1の反応物を前記基板表面上に吸着させ、
(b)前記第1の反応物の流れが停止した後に、前記反応チャンバをパージし、
(c)前記第1の反応物が前記基板表面上に吸着される間に、気相の第2の反応物を前記反応チャンバに導入し、
(d)前記基板表面上における前記第1の反応物と前記第2の反応物との間の表面反応を促して、前記ギャップを縁取る膜層を形成させるために、パルスプラズマであるプラズマに前記基板表面を暴露し、
(e)前記プラズマを消滅させ、
(f)前記反応チャンバをパージすること、
を備える方法。
適用例2:適用例1に記載の方法であって、
前記基板表面をプラズマに暴露する前記動作中における前記プラズマパルスの周波数は、約25Hzから約5000Hzの間である、方法。
適用例3:適用例2に記載の方法であって、
前記プラズマパルスの周波数は、約100Hzから約500Hzの間である、方法。
適用例4:適用例1から請求項3のいずれか一項に記載の方法であって、
前記堆積される膜は、シリコン窒化物膜又はシリコン炭窒化物膜である、方法。
適用例5:適用例1から請求項3のいずれか一項に記載の方法であって、
前記堆積される膜は、酸化物である、方法。
適用例6:適用例1から請求項5のいずれか一項に記載の方法であって、
前記動作(c)及び前記動作(d)は、少なくとも部分的に、同時に発生する、方法。
適用例7:適用例1から請求項6のいずれか一項に記載の方法であって、
前記プラズマは、容量結合プラズマ又は誘導結合プラズマである、方法。
適用例8:適用例1から請求項7のいずれか一項に記載の方法であって、
前記プラズマは、RFプラズマ発生器を使用して生成される、方法。
適用例9:適用例1から請求項8のいずれか一項に記載の方法であって、
プラズマ電力は、約50W/ステーションから約2500W/ステーションの間である、方法。
適用例10:適用例1から請求項9のいずれか一項に記載の方法であって、
前記ギャップの側壁の中間部分におけるウェットエッチング速度(WE m )と、前記ギャップの頂部におけるウェットエッチング速度(WE t )及び/又は前記ギャップの底部におけるウェットエッチング速度(WE b )との比は、約0.25から約3の間である、方法。
適用例11:適用例1から請求項10のいずれか一項に記載の方法であって、
前記ギャップ内の中間部分に形成される膜は、垂直方向に測定されたときに、約1Å/分から約25Å/分の間のウェットエッチング速度を示す、方法。
適用例12:適用例1から請求項11のいずれか一項に記載の方法であって、
前記ギャップの側壁における平均の炭素:シリコン比は、少なくとも約0.4である、方法。
適用例13:適用例1から請求項12のいずれか一項に記載の方法であって、
前記膜の組成は、前記膜全体を通じて実質的に均一である、方法。
適用例14:適用例1から請求項13のいずれか一項に記載の方法であって、更に、
前記動作(a)から前記動作(f)までを繰り返すことを備え、前記動作(d)の一度目の繰り返しは、前記動作(d)の二度目の繰り返しとは異なるパルス周波数で実施される、方法。
適用例15:適用例1から請求項14のいずれか一項に記載の方法であって、更に、
前記動作(a)から前記動作(f)までを繰り返すことを備え、前記動作(d)の一度目の繰り返しは、前記動作(d)の二度目の繰り返しとは異なるデューティサイクルで実施される、方法。
適用例16:適用例1から請求項15のいずれか一項に記載の方法であって、更に、
前記動作(a)から前記動作(f)までを繰り返すことを備え、前記動作(d)の一度目の繰り返しは、前記動作(d)の二度目の繰り返しとは異なるRF電力で実施される、方法。
適用例17:適用例1から請求項16のいずれか一項に記載の方法であって、
前記パルスプラズマは、オン状態とオフ状態との間でパルス化される、方法。
適用例18:適用例1から請求項16のいずれか一項に記載の方法であって、
前記パルスプラズマは、少なくとも第1の電力状態と第2の電力状態との間でパルス化され、前記第1の電力状態の最中に供給される電力は、前記第2の電力状態の最中に供給される電力とは異なり、前記第1の電力状態及び前記第2の電力状態のいずれも、オフ状態に対応しない、方法。
適用例19:基板上に膜を堆積させるための装置であって、
反応チャンバと、
気相の反応物を前記反応チャンバに供給するための入口と、
パルスプラズマを前記反応チャンバに提供するためのプラズマ発生器と、
コントローラであって、
(a)気相の第1の反応物を前記反応チャンバに導入するための命令と、
(b)気相の第2の反応物を前記反応チャンバに導入するための命令と、
(c)前記基板表面上における前記第1の反応物と前記第2の反応物との間の表面反応を促して、前記膜を形成させるために、前記第1の反応物の前記気相の流れが停止したときにパルスプラズマを定期的に打ち出して、前記基板表面をパルスプラズマに暴露するための命令と、
を有するコントローラと、
を備える装置。
適用例20:適用例19に記載の装置であって、
前記コントローラは、前記動作(c)の最中に約25Hzから約5000Hzの間の周波数で前記プラズマをパルス化させるための命令を有する、装置。
適用例21:適用例20に記載の装置であって、
前記コントローラは、前記動作(c)の最中に約100Hzから約500Hzの間の周波数で前記プラズマをパルス化させるための命令を有する、装置。
適用例22:適用例19から請求項21のいずれか一項に記載の装置であって、
前記コントローラは、前記動作(b)及び前記動作(c)を少なくとも部分的に同時に実施するための命令を有する、装置。
適用例23:適用例19から請求項22のいずれか一項に記載の装置であって、
前記コントローラは、前記動作(c)を約5%から約95%の間のプラズマデューティサイクルで実施するための命令を有する、装置
適用例24:適用例19から請求項23のいずれか一項に記載の装置であって、
前記コントローラは、前記動作(a)から前記動作(c)までを繰り返すための命令を有し、前記コントローラは、前記動作(c)の一度目の繰り返しを前記動作(c)の二度目の繰り返しとは異なるパルス周波数、及び/又はデューティサイクル、及び/又はRF電力で実施するための命令を有する、装置。
Claims (21)
- 半導体基板の表面上のギャップを満たす方法であって、
(a)その中に前記半導体基板を有する反応チャンバに気相の第1の反応物を導入し、前記第1の反応物を前記半導体基板の表面上に吸着させ、
(b)前記第1の反応物の流れが停止した後に、前記反応チャンバをパージし、
(c)前記第1の反応物が前記半導体基板の表面上に吸着される間に、気相の第2の反応物を前記反応チャンバに導入し、
(d)前記半導体基板の表面上における前記第1の反応物と前記第2の反応物との間の表面反応を促して、前記ギャップを縁取る膜層を形成させるために、パルスプラズマであるプラズマに前記半導体基板の表面を暴露し、
(e)前記プラズマを消滅させ、
(f)前記反応チャンバをパージすること、
動作(a)から動作(f)までを繰り返すことを備え、動作(d)の一度目の繰り返しは、動作(d)の二度目の繰り返しとは異なるパルス周波数およびデューティサイクルの少なくともいずれか一方で実施される、方法。 - 請求項1に記載の方法であって、
前記半導体基板の表面をプラズマに暴露する動作中におけるプラズマパルスの周波数は、25Hzから5000Hzの間である、方法。 - 請求項2に記載の方法であって、
前記プラズマパルスの周波数は、100Hzから500Hzの間である、方法。 - 請求項1から請求項3のいずれか一項に記載の方法であって、
堆積される前記膜層は、シリコン窒化物膜層又はシリコン炭窒化物膜層である、方法。 - 請求項1から請求項3のいずれか一項に記載の方法であって、
堆積される前記膜層は、酸化物である、方法。 - 請求項1から請求項5のいずれか一項に記載の方法であって、
動作(c)及び動作(d)は、少なくとも部分的に、同時に発生する、方法。 - 請求項1から請求項6のいずれか一項に記載の方法であって、
前記プラズマは、容量結合プラズマ又は誘導結合プラズマである、方法。 - 請求項1から請求項7のいずれか一項に記載の方法であって、
前記プラズマは、RFプラズマ発生器を使用して生成される、方法。 - 請求項1から請求項8のいずれか一項に記載の方法であって、
プラズマ電力は、50W/ステーションから2500W/ステーションの間である、方法。 - 請求項1から請求項9のいずれか一項に記載の方法であって、
前記ギャップの側壁の中間部分におけるウェットエッチング速度(WEm)と、前記ギャップの頂部におけるウェットエッチング速度(WEt)及び/又は前記ギャップの底部におけるウェットエッチング速度(WEb)との比は、0.25から3の間である、方法。 - 請求項1から請求項10のいずれか一項に記載の方法であって、
前記ギャップ内の中間部分に形成される膜層は、膜厚方向に測定されたときに、1Å/分から25Å/分の間のウェットエッチング速度を示す、方法。 - 請求項1から請求項11のいずれか一項に記載の方法であって、
前記ギャップの側壁における平均の炭素:シリコン比は、少なくとも0.4である、方法。 - 請求項1から請求項12のいずれか一項に記載の方法であって、
前記膜層の組成は、前記膜層の全体を通じて均一である、方法。 - 請求項1から請求項13のいずれか一項に記載の方法であって、更に、
動作(a)から動作(f)までを繰り返すことを備え、動作(d)の一度目の繰り返しは、動作(d)の二度目の繰り返しとは異なるRF電力で実施される、方法。 - 請求項1から請求項14のいずれか一項に記載の方法であって、
前記パルスプラズマは、オン状態とオフ状態との間でパルス化される、方法。 - 請求項1から請求項14のいずれか一項に記載の方法であって、
前記パルスプラズマは、少なくとも第1の電力状態と第2の電力状態との間でパルス化され、前記第1の電力状態の最中に供給される電力は、前記第2の電力状態の最中に供給される電力とは異なり、前記第1の電力状態及び前記第2の電力状態のいずれも、オフ状態に対応しない、方法。 - 基板上に膜を堆積させるための装置であって、
反応チャンバと、
気相の反応物を前記反応チャンバに供給するための入口と、
パルスプラズマを前記反応チャンバに提供するためのプラズマ発生器と、
コントローラであって、
(a)気相の第1の反応物を前記反応チャンバに導入するための命令と、
(b)気相の第2の反応物を前記反応チャンバに導入するための命令と、
(c)前記基板の表面上における前記第1の反応物と前記第2の反応物との間の表面反応を促して、前記膜を形成させるために、前記第1の反応物の前記気相の流れが停止したときにパルスプラズマを定期的に打ち出して、前記基板の表面をパルスプラズマに暴露するための命令と、
を有するコントローラと、を備え、前記コントローラは、動作(a)から動作(c)までを繰り返すための命令を有し、前記コントローラは、動作(c)の一度目の繰り返しを動作(c)の二度目の繰り返しとは異なるパルス周波数、及び/又はデューティサイクルで実施するための命令を有する、装置。 - 請求項17に記載の装置であって、
前記コントローラは、動作(c)の最中に25Hzから5000Hzの間の周波数でプラズマをパルス化させるための命令を有する、装置。 - 請求項18に記載の装置であって、
前記コントローラは、動作(c)の最中に100Hzから500Hzの間の周波数で前記プラズマをパルス化させるための命令を有する、装置。 - 請求項17から請求項19のいずれか一項に記載の装置であって、
前記コントローラは、動作(b)及び動作(c)を少なくとも部分的に同時に実施するための命令を有する、装置。 - 請求項17から請求項20のいずれか一項に記載の装置であって、
前記コントローラは、動作(c)を5%から95%の間のプラズマデューティサイクルで実施するための命令を有する、装置。
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KR20220076343A (ko) | 2020-11-30 | 2022-06-08 | 에이에스엠 아이피 홀딩 비.브이. | 기판 처리 장치의 반응 챔버 내에 배열되도록 구성된 인젝터 |
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TW202231903A (zh) | 2020-12-22 | 2022-08-16 | 荷蘭商Asm Ip私人控股有限公司 | 過渡金屬沉積方法、過渡金屬層、用於沉積過渡金屬於基板上的沉積總成 |
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USD980813S1 (en) | 2021-05-11 | 2023-03-14 | Asm Ip Holding B.V. | Gas flow control plate for substrate processing apparatus |
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JP5547763B2 (ja) * | 2012-03-16 | 2014-07-16 | 三井造船株式会社 | プラズマ生成方法、この方法を用いた薄膜形成方法及びプラズマ生成装置 |
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